CN113189128A - Method and device for measuring gas content of multi-component gas in pores of porous material - Google Patents

Method and device for measuring gas content of multi-component gas in pores of porous material Download PDF

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CN113189128A
CN113189128A CN202110431176.2A CN202110431176A CN113189128A CN 113189128 A CN113189128 A CN 113189128A CN 202110431176 A CN202110431176 A CN 202110431176A CN 113189128 A CN113189128 A CN 113189128A
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gas
component
section
air inlet
sample
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CN113189128B (en
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胥蕊娜
姜培学
陆韬杰
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Tsinghua University
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Tsinghua University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
    • G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
    • G01N24/082—Measurement of solid, liquid or gas content
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N7/00—Analysing materials by measuring the pressure or volume of a gas or vapour
    • G01N7/02—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder
    • G01N7/04—Analysing materials by measuring the pressure or volume of a gas or vapour by absorption, adsorption, or combustion of components and measurement of the change in pressure or volume of the remainder by absorption or adsorption alone

Abstract

The invention provides a method and a device for measuring the gas content of multi-component gas in pores of a porous material, wherein the multi-component gas comprises a hydrogen-containing gas component and a hydrogen-free gas component, and the measuring method comprises the following steps: injecting a multi-component gas into the sample segment containing the porous material; after the adsorption of the porous material in the sample section on the multi-component gas reaches adsorption equilibrium, the multi-component gas injected into the sample section forms a non-free part adsorbed into pores of the porous material and a free part not adsorbed by the porous material; obtaining the quantity of each component in the multi-component gas injected into the sample section and the proportion of the content of each component in the free state part, and obtaining the nuclear magnetic resonance transverse relaxation peak area of the hydrogen-containing gas component in the free state part through a nuclear magnetic resonance transverse relaxation test; the amount of each component in the multi-component gas adsorbed into the pores of the porous material is determined based on the measurement results. The method can quantitatively determine the competitive adsorption performance of each component under the coexistence condition of various gases.

Description

Method and device for measuring gas content of multi-component gas in pores of porous material
Technical Field
The invention relates to measurement of gas content in pores of a porous material, in particular to a method and a device for measuring gas content of multi-component gas in pores of the porous material.
Background
The measurement of the gas content in the pores of the nano-porous material is an important basis for evaluating the adsorption performance of the porous material, and for a multi-component gas consisting of at least two gases, the adsorption states of the components in the pores of the porous material are different, and the adsorption performance of the walls of the porous material facing the components is different, so that the gas content of the components in the multi-component gas in the pores of the porous material is different, and a competitive adsorption state exists. The method can accurately measure the gas content of each component in the multi-component gas in the pores of the porous material, is favorable for quantitatively evaluating the adsorption performance of the solid material (the porous material) to different gases, and has great application prospect in the fields of underground resource development, gas separation, fuel cells and the like.
Taking the development of underground unconventional natural gas as an example, in unconventional natural gas represented by shale gas and coal bed gas, methane is a main component, but unlike conventional natural gas, methane is present in nanopores of solid substances such as shale and coal, and a large amount of adsorbed gas is present in the solid substances due to adsorption on wall surfaces. In the process of developing shale gas or coal bed gas, the yield increase of carbon dioxide is an effective way, the aim of increasing the yield of natural gas is achieved by mainly utilizing the fact that the adsorption capacity of carbon dioxide on the organic wall surface is higher than that of methane and replacing methane adsorbed in pores with carbon dioxide, and in the process, how to quantitatively evaluate the competitive adsorption performance of methane and carbon dioxide in the pores under different conditions is the basis for formulating an effective development scheme.
At present, competitive adsorption performances among different gases are mainly measured by a volume method and a weight method, when the competitive adsorption performances are compared, an adsorption curve of a single gas is generally directly measured, and then adsorption curves of different gases are compared, so that the adsorption capacity of a porous material to each gas is judged.
Disclosure of Invention
The invention provides a method and a device for measuring the gas content of multi-component gas in pores of a porous material, which can be used for measuring the adsorption capacity of the porous material to each component in the porous material under the coexistence of multiple gases and effectively overcome the defects in the prior art.
In one aspect of the present invention, a method for measuring the gas content of a multi-component gas in pores of a porous material is provided, the multi-component gas comprises a hydrogen-containing gas component and a hydrogen-free gas component, and the measurement is performed by using a measurement device comprising a sample section, and the measurement method comprises: injecting a multi-component gas into the sample segment containing the porous material; after the adsorption of the porous material in the sample section on the multi-component gas reaches adsorption equilibrium, the multi-component gas injected into the sample section forms a non-free part adsorbed into pores of the porous material and a free part not adsorbed by the porous material; obtaining the quantity of each component in the multi-component gas injected into the sample section and the proportion of the content of each component in the free state part, and obtaining the nuclear magnetic resonance transverse relaxation peak area of the hydrogen-containing gas component in the free state part through a nuclear magnetic resonance transverse relaxation test; determining the amount of the hydrogen-containing gas component in the free state part based on the functional relationship between the peak area of the nuclear magnetic resonance transverse relaxation peak and the amount of the hydrogen-containing gas component in the free state; calculating and determining the amount of each component in the free state part according to the amount of the hydrogen-containing gas component in the free state part and the proportion of the content of each component in the free state part; the amount of each component in the non-free state portion is determined by calculation based on the amount of each component in the multi-component gas injected into the sample segment and the amount of each component in the free state portion.
According to one embodiment of the invention, the measuring device further comprises an air source and a measuring section, wherein the measuring section comprises an air inlet section and a sample section, the air source, the air inlet section and the sample section are sequentially connected, a first air inlet valve is arranged between the air source and the air inlet section, and a second air inlet valve is arranged between the air inlet section and the sample section; the measuring method comprises the following steps: (1) obtaining the volume V of the air intake section0(ii) a (2) Measurement of P0、T0、A0、P1、T1、Ax: (2b) maintaining second intake valve closedClosing the first air inlet valve, opening the first air inlet valve to communicate the air source with the air inlet section, injecting multi-component gas into the air inlet section through the air source, closing the first air inlet valve after the injection is finished, and acquiring the pressure P of the air inlet section after the pressure of the air inlet section is stable0Temperature T0And the ratio A of the contents of the components in the multi-component gas injected into the gas inlet section0(ii) a (2c) Opening a second air inlet valve to communicate the air inlet section with the sample section, enabling the multi-component gas of the air inlet section to flow into the sample section filled with the porous material, so as to inject the multi-component gas into the sample section, achieving adsorption balance after the pressure of the section to be measured is stable, and then obtaining the pressure P of the measuring section1And temperature T1And measuring the ratio A of the contents of the components in the free-state multi-component gas in the sectionxAnd performing a nuclear magnetic resonance transverse relaxation test; gas equation of state based on relationships characterizing pressure, volume, quantity of substance, temperature, in A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas entry segment; with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is achieved is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the amount of each component in the multi-component gas in the gas inlet section after reaching the adsorption equilibrium in the step (2 c); according to N01、Nx1Calculating and determining the amount of each component in the multi-component gas injected into the sample section; a is to bexThe amount of each component in the free state component is calculated and determined as the ratio of the content of each component in the free state portion.
According to an embodiment of the present invention, the step (1) includes: (1b) keeping the first air inlet valve closed, and obtaining the initial pressure P of the air source01Initial volume V of gas source01And the pressure P of the intake section02(ii) a (1c) Keeping the second air inlet valve closed, opening the first air inlet valve to communicate the air source with the air inlet section, injecting air into the air inlet section through the air source, and closing the first air inlet valve after the injection is finished; pressure of gas sourceAfter stabilization, the pressure P of the air source is obtained01' volume of gas source V01'; after the pressure of the air inlet section is stable, acquiring the pressure P of the air inlet section02'; (1d) according to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of the intake section0。
According to an embodiment of the present invention, the measuring apparatus further comprises a vacuum pump connected to the air intake section through an exhaust pipe provided with a vacuum valve; the step (2) comprises the following steps: keeping the first air inlet valve closed, the second air inlet valve open and the vacuum valve open, vacuumizing the measuring section through the vacuum pump, then closing the vacuum valve, and then performing the step (2 b).
According to an embodiment of the present invention, the measuring apparatus further includes a gas chromatograph, the gas inlet section includes a reference cavity, a first pipeline between the reference cavity and the first gas inlet valve, and a second pipeline between the reference cavity and the second gas inlet valve, the reference cavity is used for containing gas injected into the gas inlet section, and the gas chromatograph is connected to the second pipeline through a sample inlet pipe provided with a sample inlet valve; obtaining A0The process comprises the following steps: opening the sample injection valve to make the gas chromatograph absorb the multi-component gas in the gas inlet section and then perform gas chromatographic analysis to obtain A0(ii) a The gas inlet section is communicated with the sample section after the sample injection valve is closed; and/or, obtaining AxThe process comprises the following steps: opening the sample injection valve to make the gas chromatograph absorb the multi-component gas in the measuring section and then perform gas chromatographic analysis to obtain Ax(ii) a And closing the sample injection valve and then performing a nuclear magnetic resonance transverse relaxation test.
According to an embodiment of the present invention, the sample section includes a sample cavity, the sample cavity is used for containing a porous material, a coil for emitting electromagnetic waves for implementing the nmr transverse relaxation test to the sample cavity and a permanent magnet for providing a magnetic field environment for implementing the nmr transverse relaxation test are disposed on a housing of the sample cavity; the measuring device also comprises a controller which is connected with the shell of the sample cavity to realize the nuclear magnetic resonance transverse relaxation test; the nuclear magnetic resonance transverse relaxation test process comprises the following steps: providing a magnetic field environment for the sample cavity through the permanent magnet, and sending instructions through the controller, and sequentially carrying out the following processes: the coil emits electromagnetic waves to the sample cavity, the hydrogen-containing gas in the sample cavity returns to the controller based on signals generated by the electromagnetic waves, the controller inverts the signals to obtain a nuclear magnetic resonance transverse relaxation peak, and the peak area is determined according to the nuclear magnetic resonance transverse relaxation peak.
According to an embodiment of the present invention, the measuring device further includes a pressure sensor and a temperature sensor disposed at the air intake section, the pressure sensor being configured to detect at least a pressure of the air intake section and a pressure of the measuring section, and the temperature sensor being configured to detect at least a temperature of the air intake section and a temperature of the measuring section.
According to an embodiment of the present invention, the porous material has nanopores; and/or the porous material comprises solid materials in a shale gas layer and/or solid materials in a coal gas layer; and/or, the hydrogen-containing gas component comprises methane and/or hydrogen; and/or, the hydrogen-free gas component comprises carbon dioxide and/or nitrogen.
In another aspect of the present invention, there is provided a gas content measuring apparatus for a multi-component gas in pores of a porous material, comprising: the device comprises a gas source, a measuring section, a vacuum pump, a gas chromatograph, a controller, a pressure sensor and a temperature sensor, wherein the measuring section comprises a gas inlet section and a sample section; a first air inlet valve is arranged between the air source and the air inlet section, and a second air inlet valve is arranged between the air inlet section and the sample section; the air inlet section comprises a reference cavity, a first pipeline between the reference cavity and the first air inlet valve, and a second pipeline between the reference cavity and the second air inlet valve, and the reference cavity is used for containing air injected into the air inlet section; the gas chromatograph is connected with the second pipeline through a sample inlet pipe provided with a sample inlet valve; the sample section comprises a sample cavity for containing the porous material and a third pipeline between the sample cavity and the second air inlet valve; the shell of the sample cavity is provided with a coil for transmitting electromagnetic waves for realizing the nuclear magnetic resonance transverse relaxation test to the sample cavity and a permanent magnet for providing a magnetic field environment for realizing the nuclear magnetic resonance transverse relaxation test; the controller is connected with the shell of the sample cavity to realize the nuclear magnetic resonance transverse relaxation test; the vacuum pump is connected with the air inlet section through an exhaust pipe provided with a vacuum valve; the pressure sensor and the temperature sensor are arranged at the air inlet section, the pressure sensor is at least used for detecting the pressure of the air inlet section and the pressure of the measuring section, and the temperature sensor is at least used for detecting the temperature of the air inlet section and the temperature of the measuring section.
In another aspect of the present invention, there is provided a method for measuring the gas content of a multi-component gas in pores of a porous material, the method using the above measuring apparatus, the method comprising:
(1) determining the volume V of the intake section0: (1a) keeping the first air inlet valve and the sample injection valve closed, closing or opening the second air inlet valve, opening the vacuum valve, vacuumizing the air inlet section through a vacuum pump, and then closing the vacuum valve; (1b) keeping the first air inlet valve closed, and obtaining the initial pressure P of the air source01Initial volume V of gas source01(ii) a Keeping the first air inlet valve, the second air inlet valve, the sample injection valve and the vacuum valve closed to obtain the pressure P of the air inlet section02(ii) a (1c) Opening a first air inlet valve to communicate an air source with the air inlet section, injecting air into the air inlet section through the air source, and closing the first air inlet valve after the injection is finished; after the pressure of the air source is stable, acquiring the pressure P of the air source01' volume of gas source V01'; after the pressure of the air inlet section is stable, the pressure P of the air inlet section is obtained through the pressure sensor02'; (1d) according to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of the intake section0；
(2) Measurement of P0、T0、A0、P1、T1、Ax: (2a) keeping the first air inlet valve and the sample injection valve closed, opening the second air inlet valve, opening the vacuum valve, vacuumizing the measurement section through a vacuum pump, and then closing the vacuum valve; (2b) closing the second air inlet valve, opening the first air inlet valve to communicate the air source with the air inlet section, and injecting multi-component gas into the air inlet section through the air source; after the injection is finished, the first air inlet valve is closed, and after the pressure of the air inlet section is stabilized: opening the sample injection valve to make the gas chromatographic analyzer absorb the multi-component gas in the gas inlet section and then perform gas chromatographic analysis to obtain the proportion A of the content of each component in the multi-component gas injected into the gas inlet section0(ii) a By pressureThe sensor obtains the pressure P of the air inlet section0(ii) a Obtaining the temperature T of the air inlet section through a temperature sensor0(ii) a (2c) Closing the sample introduction valve, opening the second air inlet valve to communicate the air inlet section with the sample section, so that the multi-component gas in the air inlet section flows into the sample section containing the porous material, determining that the adsorption of the porous material in the sample cavity to the multi-component gas reaches adsorption balance after the pressure of the section to be measured is stable, forming a non-free state part adsorbed into pores of the porous material and a free state part not adsorbed by the porous material by the multi-component gas flowing into the sample section, and then: opening the sample introduction valve to enable the gas chromatographic analyzer to absorb the multi-component gas in the measurement section and then carry out gas chromatographic analysis to obtain the proportion A of the content of each component in the free multi-component gas in the measurement sectionx(ii) a Obtaining the pressure P of the measuring section by means of a pressure sensor1(ii) a Obtaining the temperature T of the measurement section by means of a temperature sensor1(ii) a Closing the sample introduction valve, and carrying out nuclear magnetic resonance transverse relaxation test on the sample cavity to obtain the peak area of the nuclear magnetic resonance transverse relaxation peak of the hydrogen-containing gas component in the free state part in the sample section;
gas equation of state based on relationships characterizing pressure, volume, quantity of substance, temperature, in A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas entry segment; with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is achieved is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the amount of each component in the multi-component gas in the gas inlet section after reaching the adsorption equilibrium in the step (2 c); according to N01、Nx1Calculating and determining the amount of each component in the multi-component gas injected into the sample section; determining the amount of hydrogen-containing gas components in the free-state part in the sample section based on the functional relationship between the peak area of the nuclear magnetic resonance transverse relaxation peak and the amount of the free-state hydrogen-containing gas; a is to bexAs a ratio of contents of the components in the free state portion to the hydrogen-containing gas in the free state portionCalculating the amount of each component in the free state part according to the amount of the component and the proportion of the content of each component in the free state part; the amount of each component in the non-free state portion is determined by calculation based on the amount of each component in the multi-component gas injected into the sample segment and the amount of each component in the free state portion.
The implementation of the invention has at least the following beneficial effects: according to the invention, based on the fact that the hydrogen-containing gas can generate signals in the hydrogen nuclear magnetic resonance and the hydrogen-free gas does not generate signals in the hydrogen nuclear magnetic resonance, the measurement process of simultaneous feeding of the multi-component gas is designed, the adsorption capacity of the porous material to each component in the multi-component gas under the condition of multi-component coexistence can be efficiently measured, the quantitative determination of the gas content of each component in the porous material is realized, the competitive adsorption performance of each component relative to the porous material under the condition of multi-component gas coexistence can be more accurately evaluated, in addition, the conditions such as temperature in the test process can be regulated and controlled, so that the adsorption performance of each component in the multi-component gas relative to the porous material under the conditions of different temperatures and the like can be determined, and the method has important significance for practical industrial application. The method can be particularly applied to the process of developing shale gas and coal bed gas, can efficiently and quantitatively evaluate the competitive adsorption performance of different gases in the pores of the shale and the coal bed under different conditions, and provides a foundation for improving the yield increase of the shale gas and the coal bed gas.
Drawings
FIG. 1 is a schematic structural diagram of a gas content measuring device for a multi-component gas in pores of a porous material according to an embodiment of the present invention;
FIG. 2 is a NMR transverse relaxation peak plot of hydrogen-containing gas species in the free-state portion as measured in an example of the present invention.
Description of reference numerals: 1. a gas source; 2. a first intake valve; 3. a pressure sensor; 4. a reference cavity; 5. a temperature sensor; 6. a vacuum valve; 7. a vacuum pump; 8. a gas chromatograph; 9. a sample injection valve; 10. a second intake valve; 11. a porous material; 12. a housing of the sample chamber; 13. a permanent magnet; 14. an air intake section; 15. a sample section; 16. and (6) measuring the section.
Detailed Description
In order that those skilled in the art will better understand the concept of the present invention, the following detailed description is given with reference to the accompanying drawings. In the present invention, the "amount" in the "amount of component", "amount of multicomponent gas" and other "amounts" indicative of quantity/content and the like may specifically be the amount of a substance, or may be mass or other parameters converted from the amount of a substance; the "content ratio" may be a molar ratio, or may be a mass ratio in terms of a molar ratio.
In the invention, the gas state equation for representing the relationship among pressure, volume, amount of substances and temperature is PV ═ ZnRT, R is a proportionality constant and is about 8.314J/(mol · K); z is a compression factor, whose magnitude reflects the degree of deviation of the real gas from the ideal gas (the gas under standard conditions), and is used to correct the ideal gas state equation (PV ═ nRT, Z ═ 1) to obtain the real gas state equation (PV ═ ZnRT), and in particular, the value of the compression factor Z corresponding to the gas under the pressure and other conditions can be searched from a database according to the gas type and the pressure and other conditions of the gas, for example, Z can be queried through a National Institute of Standards and Technology (NIST) database.
As shown in fig. 1, the present invention provides a method for measuring the gas content of a multi-component gas in pores of a porous material, wherein the multi-component gas comprises a hydrogen-containing gas component and a hydrogen-free gas component, and the measurement is performed by using a measurement apparatus comprising a sample segment 15, and the measurement method comprises: injecting a multi-component gas into the sample segment 15 containing the porous material; after the porous material in the sample section 15 achieves adsorption equilibrium to the multi-component gas, the multi-component gas injected into the sample section 15 forms a non-free part adsorbed into the pores of the porous material and a free part not adsorbed by the porous material; obtaining the amount of each component in the multi-component gas injected into the sample section 15 and the proportion of each component content in the free state part, and obtaining the nuclear magnetic resonance transverse relaxation peak area of the hydrogen-containing gas component (free state hydrogen-containing gas) in the free state part through a nuclear magnetic resonance transverse relaxation test; determining the amount of the hydrogen-containing gas component in the free state part based on the functional relationship between the peak area of the nuclear magnetic resonance transverse relaxation peak and the amount of the hydrogen-containing gas component in the free state; calculating and determining the amount of each component in the free state part according to the amount of the hydrogen-containing gas component in the free state part and the proportion of the content of each component in the free state part; the amount of each component in the non-free portion (i.e., the gas content of each component in the porous material) is determined by calculation based on the amount of each component in the multi-component gas injected into sample section 15 and the amount of each component in the free portion.
As shown in fig. 1, in some embodiments, the measuring apparatus further includes an air supply 1 and a measuring section 16, the measuring section 16 includes an air inlet section 14 and a sample section 15, the air supply 1, the air inlet section 14, and the sample section 15 are connected in sequence, a first air inlet valve 2 is disposed between the air supply 1 and the air inlet section 14, and a second air inlet valve 10 is disposed between the air inlet section 14 and the sample section 15; the gas source 1 mainly provides the gas inlet section with the multi-component gas, and may specifically include a gas cylinder containing the multi-component gas and/or a gas pump injecting the multi-component gas into the gas inlet section 14.
Specifically, the measurement method may include: (1) the volume (i.e., the volume between the first intake valve 2 and the second intake valve 10) V of the intake section 14 is obtained0(ii) a (2) Measurement of P0、T0、A0、P1、T1、Ax: (2b) keeping the second air inlet valve 10 closed, opening the first air inlet valve 2 to communicate the air source 1 with the air inlet section 14, injecting multi-component gas into the air inlet section 14 through the air source 1, closing the first air inlet valve 2 after the injection is finished, and acquiring the pressure P of the air inlet section 14 after the pressure of the air inlet section 14 is stable0Temperature T0And the ratio A of the contents of the components in the multi-component gas injected into the gas inlet section 140(ii) a (2c) Opening the second air inlet valve 10 to communicate the air inlet section 14 with the sample section 15, so that the multi-component gas in the air inlet section 14 flows into the sample section 15 filled with the porous material, thereby injecting the multi-component gas into the sample section 15, achieving adsorption balance after the pressure of the section to be measured 16 is stable, and then obtaining the pressure P of the measuring section 161And temperature T1And a ratio A of the contents of the components in the multicomponent gas in the free state in the measuring section 16xAnd performing the nuclear magnetic resonance transverse relaxation test.
In the above process, after the adsorption equilibrium is reached, the free state in the sample sectionThe state of the part is basically the same as that of the multi-component gas in the gas inlet section, namely, the content and the proportion of each component in the free-state part in the sample section are the same as those of the multi-component gas in the gas inlet section, and the pressure and the temperature of the sample section are also basically the same as those of the gas inlet section, so that the component A can be used asxAs the following multi-component gas GRear endThe content ratio of each component in the composition is defined as AxAnd as the proportion of the content of each component in the free state part, calculating and determining the adsorption quantity of the porous material of the sample section to each component according to the following process:
(I) based on the gas equation of state (PV ═ ZnRT) which characterizes the pressure, volume, quantity of substance, temperature relationships, expressed as A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas inlet section, i.e. the multi-component gas (denoted as multi-component gas G) of the gas inlet section 14 before the gas inlet section 14 communicates with the sample section 15 in step (2c)Front side) The amount of each component in (a);
in particular according to A0And P0Conversion of a multicomponent gas GFront sideThe partial pressure of each component (the proportion of the partial pressure of each component is the same as the content of each component, and the sum of the partial pressures of each component is equal to P0) Respectively checking the compression factors Z corresponding to the components under the states of the corresponding partial pressures and the like, and calculating the substance quantity n of each component according to the partial pressure, the temperature and the volume of each component and by the aid of PV (maximum partial pressure) ZnRT (maximum partial pressure) so as to obtain the multi-component gas GFront sideThe amount of each component in (a);
(II) with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is reached is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the multi-component gas (denoted as multi-component gas G) in the gas inlet section after reaching the adsorption equilibrium in step (2c)Rear end) The amount of each component in (a);
in particular according to AxAnd P1Is converted outMulticomponent gas GRear endThe partial pressure of each component (the proportion of the partial pressure of each component is the same as the content of each component, and the sum of the partial pressures of each component is equal to P1) Respectively checking the compression factors Z corresponding to the components under the states of the corresponding partial pressures and the like, and calculating the substance quantity n of each component according to the partial pressure, the temperature and the volume of each component and by the aid of PV (maximum partial pressure) ZnRT (maximum partial pressure) so as to obtain the multi-component gas GRear endThe amount of each component in (a);
(III) according to N01、Nx1The amounts of the components in the multi-component gas injected into the sample section 15 are calculated and determined, and the multi-component gas G is illustrated by taking a certain component A as an exampleFront sideThe amount of the substance of component A is N0AMulticomponent gas GRear endThe amount of the substance of component A is NxAThe amount of component A in the multi-component gas injected into sample section 15 is then N0AAnd NxAA difference of (d);
(IV) mixing A withxThe amount of each component in the free state component is calculated and determined as the ratio of the content of each component in the free state portion.
Generally, the volume of the gas inlet section 14 is fixed, i.e., the volume of the gas inlet section does not change as the multi-component gas is injected or discharged. In some embodiments, step (1) comprises: (1b) keeping the first air inlet valve 2 closed, and obtaining the initial pressure P of the air source 101Initial volume V of gas source 101And the pressure P of the intake section 1402(ii) a (1c) Keeping the second air intake valve 10 closed, opening the first air intake valve 2 to communicate the air source 1 with the air intake section 14, injecting gas (which may be a single-component gas or a mixed gas composed of at least two components, such as a multi-component gas to be measured) into the air intake section 14 through the air source 1, and closing the first air intake valve 2 after the injection is finished; after the pressure of the air source 1 is stabilized, the pressure P of the air source 1 is obtained01', volume V of gas source 101'; after the pressure of the air inlet section 14 is stabilized, the pressure P of the air inlet section 14 is obtained02'; (1d) according to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of the intake section 140。
Optionally, the air source 1 is provided with a constant volume constant pressure pump for setting the pressure and volume of the air source 1, and the pressure of the air source (such as P) can be accurately adjusted/detected by the constant volume constant pressure pump01、P01') and volume (e.g. V)01、V01’)。
In the present invention, the measurement process is generally temperature-constant, for example, measurement is performed at room temperature. In step (1), the temperature of the gas source 1 is kept equal to the temperature of the gas inlet section 14, for example by measuring the volume V of the gas inlet section 14 at room temperature0Determining the volume V of the inlet section 14 according to the above calculation formula by the pressure change of the inlet section before and after the injection of gas according to the gas equation of state representing the relationship between pressure, volume, amount of substance and temperature0。
According to the invention, the measurement section can be vacuumized, and then the multi-component gas is injected into the gas inlet section for measurement, so that the influence of gases such as oxygen on nuclear magnetic resonance measurement can be avoided, and the measurement efficiency is further improved. In some embodiments, the measuring device further comprises a vacuum pump 7, the vacuum pump 7 is connected with the air inlet section 14 through an exhaust pipe provided with a vacuum valve 6; the step (2) comprises the following steps: keeping the first air inlet valve 2 closed, the second air inlet valve 10 open and the vacuum valve 6 open, performing vacuum treatment on the measurement section 16 through the vacuum pump 7, then closing the vacuum valve 6, and then performing the step (2 b).
When step (1) is performed, a vacuum pumping process may also be performed by the vacuum pump 7, and in some embodiments, step (1) includes: keeping the first air inlet valve 2 closed, the second air inlet valve 10 closed or opened, the vacuum valve 6 opened, and performing vacuum pumping treatment on the air inlet section 14 through the vacuum pump 7, then closing the vacuum valve 6, and performing the step (1 b).
In general, when the vacuum processing is not performed, the vacuum valve 6 is kept closed.
In the present invention, the ratio of the contents of each component in the multi-component gas can be obtained by gas chromatography, for example, the above A can be obtained by gas chromatography0And AxIn particular, the gas inlet section can be communicated with a gas chromatograph, and the multi-component gas in the gas inlet section can be treatedLine gas chromatography analysis to obtain the above A0(ii) a The measuring section can be communicated with a gas chromatograph, and the multi-component gas in the measuring section is subjected to online gas chromatographic analysis to obtain the Ax。
In some embodiments, the measuring device further comprises a gas chromatograph 8, the gas inlet section 14 comprises a reference chamber 4, a first line between the reference chamber 4 and the first gas inlet valve 2, and a second line between the reference chamber 4 and the second gas inlet valve 10, and the gas chromatograph 8 is connected to the second line through a sample inlet tube provided with a sample inlet valve 9 (i.e. the gas chromatograph 8 is located on a bypass of the gas inlet section 14). The reference chamber 4 is used for containing gas injected into the gas inlet section 14, namely for providing buffer for multi-component gas released by the gas source 1 and for storing multi-component mixed gas for the sample section 15. The inlet valve is typically kept closed when the multi-component gas composition analysis is not required (as when step (2a) below is performed).
Specifically, A is obtained0The process comprises the following steps: opening the sample injection valve 9 to make the gas chromatograph 8 suck the multi-component gas of the gas inlet section 14 and then carry out gas chromatographic analysis to obtain A0(ii) a The gas inlet section 14 is communicated with the sample section 15 after the sample injection valve 9 is closed. Obtaining AxThe process comprises the following steps: opening the sample injection valve 9, allowing the gas chromatograph 8 to absorb the multi-component gas in the measurement section 16 for gas chromatographic analysis to obtain Ax(ii) a And closing the sample injection valve 9 and then performing a nuclear magnetic resonance transverse relaxation test.
In the present invention, the gas chromatograph 8 performs the gas chromatographic analysis after sucking the multi-component gas in the gas inlet section 14 or the measurement section 16, and the amount of the required multi-component gas is the sample amount (trace amount) satisfying the gas chromatographic analysis, that is, after the gas chromatograph 8 sucks the multi-component gas, the amount and composition of the multi-component gas in the gas inlet section 14 or the measurement section 16 are basically unchanged, and the gas chromatograph 8 sucks the free multi-component gas.
Optionally, the gas chromatograph 8 may include a thermal conductivity detector and/or a hydrogen flame ionization detector, and in particular, a suitable detector may be selected according to the composition of the multi-component gas.
In some embodiments, the sample section 15 includes a sample cavity, the sample cavity is used for containing a porous material (i.e. the above-mentioned porous material 11 is contained in the sample cavity), a coil for emitting electromagnetic waves for implementing the nmr transverse relaxation test to the sample cavity and a permanent magnet 13 for providing a magnetic field environment for implementing the nmr transverse relaxation test are arranged on the housing 12 of the sample cavity; the measurement apparatus further includes a controller coupled to the housing 12 of the sample chamber to perform the nmr transverse relaxation test. Under the structure system, the sample section is embedded in the nuclear magnetic resonance system, the controller sends an instruction to the nuclear magnetic resonance system, signals of hydrogen-containing gas (namely free hydrogen-containing gas) in a free state part of the sample section can be quantitatively analyzed in real time, the nuclear magnetic resonance transverse relaxation test is realized, and the content of each component inside and outside a pore of the porous material can be more conveniently and accurately measured.
Specifically, the nmr transverse relaxation test process mainly includes: the magnetic field environment is provided to the sample chamber by the permanent magnet 13 and the instructions are sent by the controller, and the following processes are carried out in sequence: the coil emits electromagnetic waves to the sample cavity, the hydrogen-containing gas in the sample cavity returns to the controller based on signals generated by the electromagnetic waves, the controller inverts the signals to obtain a nuclear magnetic resonance transverse relaxation peak, and a peak area is determined according to the nuclear magnetic resonance transverse relaxation peak (namely the peak area is obtained by integrating according to the nuclear magnetic resonance transverse relaxation peak).
For example, fig. 2 is a nmr transverse relaxation peak plot of a hydrogen-containing gas (methane) in the free-state portion, with transverse relaxation time on the abscissa and relaxation amplitude (peak intensity) on the ordinate, in accordance with an embodiment of the present invention. According to the principle of nuclear magnetic resonance, transverse relaxation time is related to the space of molecular motion, gas molecules in pores (usually nano-pores) of a porous material are limited by pore walls, the transverse relaxation time is short, and gas molecules outside the pores (namely gas molecules in a free state) have a long transverse relaxation time, so that signals of hydrogen-containing fluid inside and outside the pores in a packed bed (namely a sample section containing the porous material) can be distinguished through the transverse relaxation time, and meanwhile, the peak area S of a transverse relaxation peak is in direct proportion to the mass n of the hydrogen-containing fluid molecules in the free state, namely, the condition that S is equal to k × n is met. FIG. 2 is a graph of a nuclear magnetic resonance transverse relaxation peak mapThe peak on the right side of the dotted line represents a signal of the hydrogen-containing gas outside the pores, and the peak area S can be obtained by integrating the peak on the right side, and the relationship S between the peak area S and the amount n of the substance is calibrated to k × n (S ═ k × n, as described below)G1) The amount of material from which the hydrogen-containing gaseous component outside the pores (i.e., the hydrogen-containing gaseous component in the free-state fraction) is available; in specific implementation, for example, the specific functional relationship between S and n (i.e. k value is obtained) may be calibrated by an external standard method, which is not described in detail herein.
In the measuring process, online nuclear magnetic resonance and gas chromatography analysis are combined, and the online measurement of the adsorption capacity of each component in the multi-component gas in the porous material is more conveniently and efficiently realized according to the nuclear magnetic resonance transverse relaxation wave peak and the change of each section of pressure and component, so that the competitive adsorption performance of each component relative to the porous material can be more accurately measured.
Alternatively, the controller may be a computer (such as a desktop computer, a laptop computer, or other computer-enabled device), and the computer may be connected to the gas chromatograph 8, and the pressure sensor 3 and the temperature sensor 5 described below, for collecting data of the multi-component gas composition, temperature, pressure, and the like.
As shown in fig. 1, the intake section 14 is a portion from the first intake valve 2 to the second intake valve 10, i.e., the intake section 14 includes the reference chamber 4, a first conduit between the reference chamber 4 and the first intake valve 2, and a second conduit between the reference chamber 4 and the second intake valve 10; the sample section 15 is the part from the second inlet valve 10 to the sample chamber, i.e. the sample section 15 comprises the sample chamber and a third line between the sample chamber and the second inlet valve 10. Wherein, the pipe line (sealed pipeline) is used for communicating each part (such as the reference cavity 4 and the sample cavity, etc. through the second pipe line and the third pipe line), and the volume of the contained gas is very small, for example, the volume of the first pipe line and the volume of the second pipe line are basically negligible relative to the volume of the reference cavity 4 (namely, the volume of the gas inlet section is basically equal to the volume of the reference cavity), and the volume of the third pipe line is basically negligible relative to the volume of the sample cavity (namely, the volume of the sample section is basically equal to the volume of the sample cavity).
The above-mentioned valves (such as the first air intake valve, the second air intake valve, the vacuum valve, the sample injection valve, etc.) are used to realize the communication (valve opening) or the closing (valve closing) between the sections, taking the second air intake valve as an example for illustration, when the second air intake valve 10 is opened, the air source 1 is communicated with the air intake section 14, and when the second air intake valve 10 is closed, the air source 1 is closed (i.e. not communicated with the air intake section 14).
In some embodiments, the measuring device further comprises a pressure sensor 3 and a temperature sensor 5 arranged at the air intake section 14, wherein the pressure sensor 3 is at least used for detecting the pressure of the air intake section 14 and the pressure of the measuring section 16, judging whether a steady state is reached or not, and the like, and the temperature sensor 5 is at least used for detecting the temperature of the air intake section 14 and the temperature of the measuring section 16.
Alternatively, the pressure sensor 3 may be arranged above the orifice of the reference chamber 4 in particular to detect the pressure of the gas in the reference chamber 4, the gas inlet section 14, and the measurement section 16 or the sample section 15 when communicating with the reference chamber 4. The temperature sensor 5 may be disposed above the orifice of the reference chamber 4 for detecting the temperature of the reference chamber 4, the gas inlet section 14, and the gas in the measurement section 16 or the sample section 15 when in communication with the reference chamber 4.
The present invention may employ temperature sensors and pressure sensors that are conventional in the art, for example, the temperature sensors may include platinum resistance temperature sensors or the like.
Alternatively, the material of the housing (cavity) of the reference cavity 4 may be stainless steel. The housing of the sample chamber is equivalent to a sample box with a sample chamber, and is fixed in the permanent magnet 13, and the material of the housing is a non-metal pressure-resistant material, and the non-metal pressure-resistant material includes, for example, ceramic and/or polyetheretherketone. The pipeline between each section (the first pipeline and the second pipeline)
The method disclosed by the invention is applied to the development process of shale gas and coal bed gas, can efficiently and quantitatively evaluate the competitive adsorption performance of different gases in the pores of the shale and the coal bed gas under different conditions, and provides more accurate basic support for improving the yield increase of the shale gas and the coal gas.
Generally, the porous material may be in a granular form, and in particular, the porous material may be ground into particles with a uniform size and/or screened through a screen to obtain a porous material consisting of particles with a preset mesh number, and then the porous material is subjected to vacuum desorption treatment, and then placed in a sample chamber, and then a shell of the sample chamber is fixed in a permanent magnet of a nuclear magnetic resonance system for measurement. The porous material is subjected to vacuum desorption treatment, so that gas adsorbed in the porous material can be removed as much as possible, the influence of gas components adsorbed in the porous material is avoided, the measurement efficiency and the accuracy of a measurement result are further improved, and the vacuum desorption treatment can be performed according to a conventional method in the field and is not repeated. The porous material typically fills the sample cavity, forming a stack within the sample cavity.
The nuclear magnetic resonance transverse relaxation test specifically comprises a hydrogen nuclear magnetic resonance test, wherein the multi-component gas is a mixed gas formed by mixing a plurality of gases, namely at least two gases, at least one hydrogen-containing gas and one hydrogen-free gas, the hydrogen-containing gas can generate signals in the hydrogen nuclear magnetic resonance, and the hydrogen-free gas can not generate signals in the hydrogen nuclear magnetic resonance. Specifically, in some embodiments, the hydrogen-containing gas component can include methane and/or hydrogen, and the hydrogen-free gas component can include carbon dioxide and/or nitrogen.
As shown in fig. 1, the present invention provides a gas content measuring apparatus for a multi-component gas in pores of a porous material, comprising: the device comprises a gas source 1, a measuring section 16, a vacuum pump 7, a gas chromatograph 8, a controller, a pressure sensor 3 and a temperature sensor 5, wherein the measuring section 16 comprises a gas inlet section 14 and a sample section 15;
a first air inlet valve 2 is arranged between the air source 1 and the air inlet section 14, and a second air inlet valve 10 is arranged between the air inlet section 14 and the sample section 15;
the gas inlet section 14 comprises a reference cavity 4, a first pipeline between the reference cavity 4 and the first gas inlet valve 2, and a second pipeline between the reference cavity 4 and the second gas inlet valve 10, wherein the reference cavity 4 is used for containing gas injected into the gas inlet section 14;
the gas chromatograph 8 is connected with a second pipeline through a sample inlet pipe provided with a sample inlet valve 9;
the sample section 15 comprises a sample chamber for containing the porous material and a third conduit between the sample chamber and the second air inlet valve 10; a coil used for emitting electromagnetic waves for realizing the nuclear magnetic resonance transverse relaxation test to the sample cavity and a permanent magnet 13 used for providing a magnetic field environment for realizing the nuclear magnetic resonance transverse relaxation test are arranged on the shell 12 of the sample cavity;
the controller is connected with the shell 12 of the sample cavity to realize the transverse relaxation test of the nuclear magnetic resonance;
the vacuum pump 7 is connected with the air inlet section 14 through an exhaust pipe provided with a vacuum valve 6;
the pressure sensor 3 and the temperature sensor 5 are arranged at the air inlet section 14, the pressure sensor 3 is at least used for detecting the pressure of the air inlet section 14 and the pressure of the measuring section 16, and the temperature sensor 5 is at least used for detecting the temperature of the air inlet section 14 and the temperature of the measuring section 16;
a measurement method according to an embodiment of the present invention is a measurement method using a measurement apparatus shown in fig. 1, the measurement method including:
(1) determining the volume V of the intake section 140：
(1a) Keeping the first air inlet valve 2 and the sample injection valve 9 closed, the second air inlet valve 10 closed or opened, the vacuum valve 6 opened, performing vacuum-pumping treatment on the air inlet section 14 through the vacuum pump 7, and then closing the vacuum valve 6;
(1b) keeping the first air inlet valve 2 closed, and obtaining the initial pressure P of the air source 101Initial volume V of gas source 101；
Keeping the first air inlet valve 2, the second air inlet valve 10, the sample injection valve 9 and the vacuum valve 6 closed, and acquiring the pressure P of the air inlet section 1402；
(1c) Opening the first air inlet valve 2 to communicate the air source 1 with the air inlet section 14, injecting air into the air inlet section 14 through the air source 1, and closing the first air inlet valve 2 after the injection is finished;
after the pressure of the air source 1 is stabilized, the pressure P of the air source 1 is obtained01', volume V of gas source 101’；
To be admitted with airAfter the pressure of the section 14 is stabilized, the pressure P of the air inlet section 14 is obtained by the pressure sensor 302’；
(1d) According to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of the intake section 140；
(2) Measurement of P0、T0、A0、P1、T1、Ax：
(2a) Keeping the first air inlet valve 2 and the sample injection valve 9 closed, opening the second air inlet valve 10, opening the vacuum valve 6, vacuumizing the measurement section 16 through the vacuum pump 7, and then closing the vacuum valve 6;
(2b) closing the second air inlet valve 10, opening the first air inlet valve 2 to communicate the air source 1 with the air inlet section 14, and injecting the multi-component gas into the air inlet section 14 through the air source 1; after the injection is finished, the first air intake valve 2 is closed, and after the pressure of the air intake section 14 is stabilized:
opening the sample injection valve 9, allowing the gas chromatographic analyzer to absorb the multi-component gas in the gas inlet section 14 and then performing gas chromatographic analysis to obtain the ratio A of the content of each component in the multi-component gas injected into the gas inlet section 140；
The pressure P of the intake section 14 is detected by the pressure sensor 30(the pressure sensor 3 has a reference P0)；
The temperature T of the intake section 14 is obtained by the temperature sensor 50(the index of the temperature sensor 5 is T0)；
(2c) Closing the sample injection valve 9, opening the second gas inlet valve 10 to communicate the gas inlet section 14 with the sample section 15, so that the multi-component gas in the gas inlet section 14 flows into the sample section 15 containing the porous material, after the pressure of the section 16 to be measured is stabilized, it is determined that the adsorption of the porous material in the sample cavity to the multi-component gas reaches adsorption equilibrium, the multi-component gas flowing into the sample section 15 forms a non-free-state part adsorbed into the pores of the porous material and a free-state part not adsorbed by the porous material, and then:
opening the sample injection valve 9 to make the gas chromatographic analyzer suck the multi-component gas in the measuring section 16 for gas chromatographic analysis to obtain a measured gasRatio A of the contents of the components in the free-state multi-component gas in the metering section 16x；
The pressure P of the measuring section 16 is obtained by the pressure sensor 31(the pressure sensor 3 has a reference P1)；
The temperature T of the measuring section 16 is obtained by the temperature sensor 51(the index of the temperature sensor 5 is T1)；
Closing the sample injection valve 9, and performing a nuclear magnetic resonance transverse relaxation test on the sample cavity to obtain the peak area of the nuclear magnetic resonance transverse relaxation peak of the hydrogen-containing gas component in the free state part in the sample section 15;
gas equation of state based on relationships characterizing pressure, volume, quantity of substance, temperature, in A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas entry segment;
with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is reached is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the amount of each component in the multi-component gas in the gas inlet section after reaching the adsorption equilibrium in step (2 c);
according to N01、Nx1Calculating and determining the amount of each component in the multi-component gas injected into the sample section 15;
determining the amount of hydrogen-containing gas components in the free-state portion within the sample segment 15 based on a functional relationship of the nmr transverse relaxation peak area and the amount of free-state hydrogen-containing gas;
a is to bexAs the proportion of the content of each component in the free state part, the amount of each component in the free state part is determined by calculation according to the amount of the hydrogen-containing gas component in the free state part and the proportion of the content of each component in the free state part;
the amount of each component in the non-free portion (i.e., the amount of each component adsorbed into the pores of the porous material) is determined by calculation based on the amount of each component in the multi-component gas injected into sample section 15, the amount of each component in the free portion.
For example, in some embodiments, the multi-component gas consists of component G1And component G2Composition G1Is a hydrogen-containing gas (e.g., methane), G2 is a non-hydrogen-containing gas (e.g., carbon dioxide);
A0denotes a multi-component gas GFront sideMiddle component G1And component G2In a molar ratio of xG1：xG2；
Multicomponent gas GFront sideMiddle component G1Partial pressure P ofG1＝P0×xG1/(xG1+xG2)；
Multicomponent gas GFront sideMiddle component G2Partial pressure P ofG2＝P0×xG2/(xG1+xG2)；
Finding the component G1At a pressure of PG1Temperature of T0Corresponding compression factor Z in stateG1；
Finding the component G2At a pressure of PG2Temperature of T0Corresponding compression factor Z in stateG2；AxDenotes a multi-component gas GRear endMiddle component G1And component G2Molar ratio xG1’：xG2' (also component G in the free part)1And component G2Molar ratio); multicomponent gas GRear endMiddle component G1Partial pressure P ofG1’＝P1×xG1’/(xG1’+xG2’)；
Multicomponent gas GRear endMiddle component G2Partial pressure P ofG2’＝P1×xG2’/(xG1’+xG2’)；
Finding the component G1At a pressure of PG1', temperature is T1Corresponding compression factor Z in stateG1’；
Finding the component G2At a pressure of PG2', temperature is T1Corresponding compression factor Z in stateG2’；
N0Denotes a multi-component gas GFront sideThe amount of each component (amount of substance): component G1The amount of substance(s) is NG1Component G2The amount of substance(s) is NG2；
NxDenotes a multi-component gas GRear endThe amount of each component (amount of substance): component G1The amount of substance(s) is NG1', component G2The amount of substance(s) is NG2’；
Amount of each component (amount of substance) in the multi-component gas injected into sample section 15: component G1The amount of substance(s) is NG1", component G2The amount of substance(s) is NG2”；
Then:
NG1＝PG1V0/ZG1RT0；
NG2＝PG2V0/ZG2RT0；
NG1’＝PG1’V0/ZG1’RT1；
NG2’＝PG2’V0/ZG2’RT1；
NG1”＝NG1-NG1’；
NG2”＝NG2-NG2’；
based on component G1Peak area S and component G of transverse relaxation peak of nuclear magnetic resonance1Amount of substance(s) nG1Is k × nG1According to S ═ kXNG1freeCalculating to obtain the component G in the free state part1(i.e. component G in the free state1) Amount of substance(s) NG1free；
According to NG2free＝NG1free×(xG2’/xG1') component G in the free fraction was calculated2(i.e. component G in the free state2) Amount of substance(s) NG2free；
According to NG1 adsorption＝NG1”-NG1freeCalculating to obtain the component G adsorbed into the pores of the porous material1(i.e.component G in a non-free state)1) Amount of substance(s) NG1 adsorption；
According to NG2 adsorption＝NG2”-NG2freeCalculating to obtain the component G adsorbed into the pores of the porous material2(i.e.component G in a non-free state)2) Amount of substance(s) NG2 adsorption。
In other embodiments, the multi-component gas consists of component G1Component G2And component G3Composition G1Is a hydrogen-containing gas, G2 is a hydrogen-free gas, G3 is another hydrogen-free gas;
A0denotes a multi-component gas GFront sideMiddle component G1Component G2And component G3Ratio of contents (molar ratio) xG1：xG2：xG3；
Multicomponent gas GFront sideMiddle component G1Partial pressure P ofG1＝P0×xG1/(xG1+xG2+xG3)；
Multicomponent gas GFront sideMiddle component G2Partial pressure P ofG2＝P0×xG2/(xG1+xG2+xG3)；
Multicomponent gas GFront sideMiddle component G3Partial pressure P ofG3＝P0×xG3/(xG1+xG2+xG3)；
Finding the component G1At a pressure of PG1Temperature of T0Corresponding compression factor Z in stateG1；
Finding the component G2At a pressure of PG2Temperature of T0Corresponding compression factor Z in stateG2；
Finding the component G3At a pressure of PG3Temperature of T0Corresponding compression factor Z in stateG3；
AxDenotes a multi-component gas GRear endMiddle component G1Component G2And component G3Ratio of contents (molar ratio) xG1’：xG2’：xG3' (also component G in the free part)1Component G2And component G3Molar ratio of (a);
multicomponent gas GRear endMiddle component G1Partial pressure P ofG1’＝P1×xG1’/(xG1’+xG2’+xG3’)；
Multicomponent gas GRear endMiddle component G2Partial pressure P ofG2’＝P1×xG2’/(xG1’+xG2’+xG3’)；
Multicomponent gas GRear endMiddle component G3Partial pressure P ofG3’＝P1×xG3’/(xG1’+xG2’+xG3’)；
Finding the component G1At a pressure of PG1', temperature is T1Corresponding compression factor Z in stateG1’；
Finding the component G2At a pressure of PG2', temperature is T1Corresponding compression factor Z in stateG2’；
Finding the component G3At a pressure of PG3Temperature of T1Corresponding compression factor Z in stateG3’；
N0Denotes a multi-component gas GFront sideThe amount of each component (amount of substance): component G1The amount of substance(s) is NG1Component G2The amount of substance(s) is NG2Component G3The amount of substance(s) is NG3；
NxDenotes a multi-component gas GRear endThe amount of each component (amount of substance): component G1The amount of substance(s) is NG1', component G2The amount of substance(s) is NG2', component G3The amount of substance(s) is NG3’；
Amount of each component (amount of substance) in the multi-component gas injected into sample section 15: component G1The amount of substance(s) is NG1", component G2The amount of substance(s) is NG2", component G3The amount of substance(s) is NG3”；
Then:
NG1＝PG1V0/ZG1RT0；
NG2＝PG2V0/ZG2RT0；
NG3＝PG3V0/ZG3RT0；
NG1’＝PG1’V0/ZG1’RT1；
NG2’＝PG2’V0/ZG2’RT1；
NG3’＝PG3’V0/ZG3’RT1；
NG1”＝NG1-NG1’；
NG2”＝NG2-NG2’；
NG3”＝NG3-NG3’；
based on component G1Peak area S and component G of transverse relaxation peak of nuclear magnetic resonance1Amount of substance(s) nG1Is k × nG1According to S ═ kXNG1freeCalculating to obtain the component G in the free state part1Amount of substance(s) NG1free；
According to NG2free＝NG1free×(xG2’/xG1') component G in the free fraction was calculated2Amount of substance(s) NG2free；
According to NG3free＝NG1free×(xG3’/xG1') component G in the free fraction was calculated3Amount of substance(s) NG3free；
According to NG1 adsorption＝NG1”-NG1freeCalculating to obtain the adsorption in the pores of the porous materialComponent G of1Amount of substance(s) NG1 adsorption；
According to NG2 adsorption＝NG2”-NG2freeCalculating to obtain the component G adsorbed into the pores of the porous material2Amount of substance(s) NG2 adsorption；
According to NG3 adsorption＝NG3”-NG3freeCalculating to obtain the component G adsorbed into the pores of the porous material3Amount of substance(s) NG3 adsorption。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for measuring the gas content of a multi-component gas in the pores of a porous material, wherein the multi-component gas comprises a hydrogen-containing gas component and a hydrogen-free gas component, and the measurement is performed by using a measuring device comprising a sample section, and the measuring method comprises the following steps:
injecting a multi-component gas into the sample segment containing the porous material;
after the adsorption of the porous material in the sample section on the multi-component gas reaches adsorption equilibrium, the multi-component gas injected into the sample section forms a non-free part adsorbed into pores of the porous material and a free part not adsorbed by the porous material;
obtaining the amount of each component in the multi-component gas injected into the sample section and the content ratio of each component in the free state part, and obtaining the peak area of the nuclear magnetic resonance transverse relaxation peak of the hydrogen-containing gas component in the free state part through a nuclear magnetic resonance transverse relaxation test;
determining the amount of hydrogen-containing gas component in the free state fraction based on a nmr transverse relaxation peak area as a function of the amount of the hydrogen-containing gas component in the free state;
calculating and determining the amount of each component in the free state part according to the amount of the hydrogen-containing gas component in the free state part and the proportion of the content of each component in the free state part;
the amount of each component in the non-free state portion is determined by calculation based on the amount of each component in the multi-component gas injected into the sample segment and the amount of each component in the free state portion.
2. The measuring method according to claim 1,
the measuring device also comprises an air source and a measuring section, wherein the measuring section comprises an air inlet section and a sample section, the air source, the air inlet section and the sample section are sequentially connected, a first air inlet valve is arranged between the air source and the air inlet section, and a second air inlet valve is arranged between the air inlet section and the sample section;
the measuring method comprises the following steps:
(1) obtaining the volume V of the air inlet section0；
(2) Measurement of P0、T0、A0、P1、T1、Ax：
(2b) Keeping the second air inlet valve closed, opening the first air inlet valve to communicate an air source with the air inlet section, injecting multi-component gas into the air inlet section through the air source, closing the first air inlet valve after injection is finished, and acquiring the pressure P of the air inlet section after the pressure of the air inlet section is stable0Temperature T0And the ratio A of the contents of the components in the multi-component gas injected into the gas inlet section0；
(2c) Opening a second air inlet valve to communicate the air inlet section with the sample section, enabling the multi-component gas of the air inlet section to flow into the sample section filled with the porous material, so as to inject the multi-component gas into the sample section, achieving the adsorption balance after the pressure of the section to be measured is stable, and then obtaining the pressure P of the measuring section1And temperature T1And measuring the ratio A of the contents of the components in the free-state multi-component gas in the sectionxAnd performing the NMR transverse relaxation test;
gas equation of state based on relationships characterizing pressure, volume, quantity of substance, temperature, in A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas entry segment;
with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is reached is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the amount of each component in the multi-component gas in the gas inlet section after reaching the adsorption equilibrium in step (2 c);
according to N01、Nx1Calculating and determining the amount of each component in the multi-component gas injected into the sample section;
a is to bexAnd calculating and determining the amount of each component in the free state component as the proportion of the content of each component in the free state part.
3. The measurement method according to claim 2, wherein step (1) comprises:
(1b) keeping the first air inlet valve closed, and obtaining the initial pressure P of the air source01Initial volume V of gas source01And the pressure P of the intake section02；
(1c) Keeping the second air inlet valve closed, opening the first air inlet valve to communicate the air source with the air inlet section, injecting air into the air inlet section through the air source, and closing the first air inlet valve after the injection is finished;
after the pressure of the air source is stable, acquiring the pressure P of the air source01' volume of gas source V01’；
After the pressure of the air inlet section is stable, acquiring the pressure P of the air inlet section02’；
(1d) According to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of said intake section0。
4. The measuring method according to claim 2 or 3,
the measuring device also comprises a vacuum pump, and the vacuum pump is connected with the air inlet section through an exhaust pipe provided with a vacuum valve;
the step (2) comprises the following steps: keeping the first air inlet valve closed, the second air inlet valve open and the vacuum valve open, vacuumizing the measuring section through the vacuum pump, then closing the vacuum valve, and then performing the step (2 b).
5. The measuring method according to any one of claims 2 to 4,
the gas chromatograph comprises a gas inlet section, a gas inlet section and a gas outlet section, wherein the gas inlet section comprises a reference cavity, a first pipeline between the reference cavity and the first gas inlet valve, and a second pipeline between the reference cavity and the second gas inlet valve;
obtaining the A0The process comprises the following steps: opening a sample injection valve to enable a gas chromatograph to absorb multi-component gas of a gas inlet section and then perform gas chromatographic analysis to obtain A0(ii) a The gas inlet section is communicated with the sample section after the sample injection valve is closed;
and/or the presence of a gas in the gas,
obtaining the AxThe process comprises the following steps: opening a sample injection valve to enable a gas chromatograph to absorb the multi-component gas of the measurement section and then carry out gas chromatography analysis to obtain the Ax(ii) a And closing the sample injection valve and then performing the nuclear magnetic resonance transverse relaxation test.
6. The measuring method according to any one of claims 1 to 5,
the sample section comprises a sample cavity, the sample cavity is used for containing the porous material, and a coil used for transmitting electromagnetic waves for realizing the nuclear magnetic resonance transverse relaxation test to the sample cavity and a permanent magnet used for providing a magnetic field environment for realizing the nuclear magnetic resonance transverse relaxation test are arranged on a shell of the sample cavity; the measuring device also comprises a controller which is connected with the shell of the sample cavity to realize the nuclear magnetic resonance transverse relaxation test;
the nuclear magnetic resonance transverse relaxation test process comprises the following steps: providing a magnetic field environment for the sample cavity through the permanent magnet, and sending instructions through the controller, and sequentially carrying out the following processes: the coil emits electromagnetic waves to the sample cavity, hydrogen-containing gas in the sample cavity returns to the controller based on signals generated by the electromagnetic waves, the controller inverts the signals to obtain the nuclear magnetic resonance transverse relaxation peak, and the peak area is determined according to the nuclear magnetic resonance transverse relaxation peak.
7. The measurement method according to any one of claims 2 to 4, wherein the measurement device further comprises a pressure sensor and a temperature sensor provided at an intake section, the pressure sensor being configured to detect at least a pressure of the intake section and a pressure of the measurement section, and the temperature sensor being configured to detect at least a temperature of the intake section and a temperature of the measurement section.
8. The measurement method according to claim 1, wherein the porous material has a nano-scale pore;
and/or the presence of a gas in the gas,
the porous material comprises solid materials in a shale gas layer and/or solid materials in a coal gas layer;
and/or the presence of a gas in the gas,
the hydrogen-containing gas component comprises methane and/or hydrogen;
and/or the presence of a gas in the gas,
the hydrogen-free gas component includes carbon dioxide and/or nitrogen.
9. An apparatus for measuring the gas content of a multi-component gas in the pores of a porous material, comprising: the device comprises a gas source, a measuring section, a vacuum pump, a gas chromatograph, a controller, a pressure sensor and a temperature sensor, wherein the measuring section comprises a gas inlet section and a sample section;
a first air inlet valve is arranged between the air source and the air inlet section, and a second air inlet valve is arranged between the air inlet section and the sample section;
the air inlet section comprises a reference cavity, a first pipeline between the reference cavity and the first air inlet valve and a second pipeline between the reference cavity and the second air inlet valve, and the reference cavity is used for containing air injected into the air inlet section;
the gas chromatograph is connected with the second pipeline through a sample inlet pipe provided with a sample inlet valve;
the sample section comprises a sample cavity for containing the porous material and a third pipeline between the sample cavity and the second air inlet valve; the shell of the sample cavity is provided with a coil for transmitting electromagnetic waves for realizing the nuclear magnetic resonance transverse relaxation test to the sample cavity and a permanent magnet for providing a magnetic field environment for realizing the nuclear magnetic resonance transverse relaxation test;
the controller is connected with the shell of the sample cavity to realize the nuclear magnetic resonance transverse relaxation test;
the vacuum pump is connected with the air inlet section through an exhaust pipe provided with a vacuum valve;
the pressure sensor and the temperature sensor are arranged at an air inlet section, the pressure sensor is at least used for detecting the pressure of the air inlet section and the pressure of the measuring section, and the temperature sensor is at least used for detecting the temperature of the air inlet section and the temperature of the measuring section.
10. A method for measuring the gas content of a multi-component gas in pores of a porous material, wherein the measurement is performed by using the measurement device of claim 9, and the method comprises the following steps:
(1) determining the volume V of said intake section0：
(1a) Keeping the first air inlet valve and the sample injection valve closed, closing or opening the second air inlet valve, opening the vacuum valve, vacuumizing the air inlet section through a vacuum pump, and then closing the vacuum valve;
(1b) keeping the first air inlet valve closed, and obtaining the initial pressure P of the air source01Initial volume V of gas source01；
Keeping the first air inlet valve, the second air inlet valve, the sample injection valve and the vacuum valve closed to obtain the pressure P of the air inlet section02；
(1c) Opening a first air inlet valve to communicate an air source with an air inlet section, injecting air into the air inlet section through the air source, and closing the first air inlet valve after the injection is finished;
after the pressure of the air source is stable, acquiring the pressure P of the air source01' volume of gas source V01’；
After the pressure of the air inlet section is stable, the pressure P of the air inlet section is obtained through the pressure sensor02’；
(1d) According to P01×V01-P01’×V01’＝P02×V0-P02’×V0Determining the volume V of said intake section0；
(2) Measurement of P0、T0、A0、P1、T1、Ax：
(2a) Keeping the first air inlet valve and the sample injection valve closed, opening the second air inlet valve, opening the vacuum valve, vacuumizing the measurement section through a vacuum pump, and then closing the vacuum valve;
(2b) closing the second air inlet valve, opening the first air inlet valve to communicate the air source with the air inlet section, and injecting the multi-component gas into the air inlet section through the air source; after the injection is finished, closing the first air inlet valve, and after the pressure of the air inlet section is stabilized:
opening a sample injection valve to enable a gas chromatographic analyzer to absorb the multi-component gas in the gas inlet section and then carry out gas chromatographic analysis to obtain the proportion A of the content of each component in the multi-component gas injected into the gas inlet section0；
Obtaining the pressure P of the air inlet section by a pressure sensor0；
Obtaining the temperature T of the air inlet section through a temperature sensor0；
(2c) Closing the sample introduction valve, opening the second air inlet valve to communicate the air inlet section with the sample section, so that the multi-component gas in the air inlet section flows into the sample section containing the porous material, determining that the adsorption of the porous material in the sample cavity to the multi-component gas reaches adsorption balance after the pressure of the section to be measured is stable, forming a non-free state part adsorbed into pores of the porous material and a free state part not adsorbed by the porous material by the multi-component gas flowing into the sample section, and then:
opening a sample injection valve to enable a gas chromatographic analyzer to absorb the multi-component gas in the measurement section and then carry out gas chromatographic analysis to obtain the proportion A of the content of each component in the free multi-component gas in the measurement sectionx；
Obtaining the pressure P of the measuring section by means of a pressure sensor1；
Obtaining the temperature T of the measurement section by means of a temperature sensor1；
Closing the sample introduction valve, and carrying out nuclear magnetic resonance transverse relaxation test on the sample cavity to obtain the peak area of the nuclear magnetic resonance transverse relaxation peak of the hydrogen-containing gas component in the free state part in the sample section;
gas equation of state based on relationships characterizing pressure, volume, quantity of substance, temperature, in A0、V0、P0、T0Calculating to determine N0，N0The meaning of (A) is: the amount of each component in the multi-component gas injected into the gas entry segment;
with AxThe proportion of each component content in the multi-component gas in the gas inlet section after the adsorption equilibrium is reached is based on a gas state equation representing the relationship among pressure, volume, quantity of substances and temperature, and is expressed as Ax、V0、P1、T1Calculating to determine Nx，NxThe meaning of (A) is: the amount of each component in the multi-component gas in the gas inlet section after reaching the adsorption equilibrium in step (2 c);
according to N01、Nx1Calculating and determining the amount of each component in the multi-component gas injected into the sample section;
determining the amount of hydrogen-containing gas components in the free-state part in the sample section based on the functional relationship between the peak area of the nuclear magnetic resonance transverse relaxation peak and the amount of the free-state hydrogen-containing gas;
a is to bexAs the proportion of the content of each component in the free state part, calculating and determining the amount of each component in the free state part according to the amount of the hydrogen-containing gas component in the free state part and the proportion of the content of each component in the free state part;
the amount of each component in the non-free state portion is determined by calculation based on the amount of each component in the multi-component gas injected into the sample segment and the amount of each component in the free state portion.
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